Detergent sulphonic acid and sulphate salts of certain amphoteric detergents



United States Patent 0 DETERGENT SULPHONIC ACID AND SUL- PHATE SALTS OFCERTAIN AMPHOTERIC DETERGENTS Hans S. Mannheimer, New York, N. Y.

No Drawing. Application February 14, 1956, Serial No. 565,307

8 Claims. (Cl. 260-401) This invention relates to novel compositions andto methods for producing them. In one of its more specific aspects, theinvention is directed to the method of making and to novel derivates ofmetal salts of substituted amido, amino acids, to which I shallhereinafter refer to as amino acid metal salts.

Said amino acid metal salts have been found useful as detergent,foaming, wetting, emulgating, emulsifying and dispersing agents. Theyare surface active agents, and serve as excellent synthetic detergents,dye assistants and softeners in the textile and related fields.

Said amino acid metal salts, employed as starting materials in thepractice of this invention, have the following general Formula I:

in which R is an organic radical, which, if connected to a carboxylgroup, provides a monocarboxylic acid, and said radical contains atleast 4 carbon atoms and for most purposes is a hydrocarbon radical of4-18 carbon atoms; R1 is hydrogen or an aliphatic hydrocarbon radicalhaving 1-4 carbon atoms, such as CH:;, C2H5, C3H7, and C4H9 or any oneof said radicals having one or more of the hydrogens thereof which hasbeen hydroxy substituted, illustrative examples of which are C2H4OH,

-CH2CHOHCH3, CHOHCHOHCH2OH or any one of said radicals, but of 2-4carbon atoms and whose hydrogens have been either unsubstituted orhydroxy substituted and having at least one ether O) and/or keto (CO)linkage therein, illustrative examples of which are --C2H4OCH3,

CH2OH-COC2H5; R2 is a hydrocarbon group having 1-4 carbon atoms, such as-CH2, C2H4, C3Hs and -C4Hs-, or any one of the aforesaid groups, any oneor more of whose hydrogens has been hydroxy substituted, illustrativeexamples of which are CH2CHOHCH2-, CH2CHOHCHOHCH2, and such hydrocarbongroups, wherein one or more of the hydrogen atoms thereof have beenhydroxy substituted, or any one of said groups, but of 2-4 carbon atomsand whose hydrogens have been either unsubstituted or hydroxysubstituted and having at least one ether (O-) and/or keto (-CO-)linkage therein; M is a metal and preferably an alkali metal and, formost purposes, is sodium or potassium.

Said amino acid metal salts may be produced in a number of differentways:

One of the methods which may be employed is to first react an hydroxydiamine with an organic acid in the molecular proportion of 1 to 1. Whenapproximately 1 mole proportion of water of reaction has been formed andthe acid number of the mass is zero, the reaction is terminated, and theresulting reaction mass under specific and controlled conditions isreacted with a metal salt of a monohalomonocarboxylic acid to provide anamino acid metal salt defined in Formula I.

The organic acid reacted with said hydroxy diamine is one containing asingle COOH group or any of the available anhydrides or" said acids andby the term monocarboxylic organic acid as used herein, I mean toinclude both the acid and the anhydride thereof which I regard as theequivalent of the acid. These acids may be: the aliphatic open chainsaturated or unsaturated fatty acids as well as said fatty acidscontaining hydroxy or keto groups and/or other substituents, such asaryl radicals, as for example, acids of the type of Twitchell fattyacids; cycloaliphatic carboxylic acids preferably containing no morethan 4 condensed nuclei and examples of WhlCll are hexahydrobenzoic,resinic, and naphthenic acids; heterocyclic aliphatic carboxylic acids,such as the various pyridine carboxylic acids.

While carboxylic acids having any number of carbon atoms may beemployed, I prefer to employ those having at least 5 carbon atoms andpreferably 5-19 carbon atoms in straight chain relationship. The acidswhich I employ may be derived from a number of different sources. Amongsome of them are the acid components chosen from oil or fats of animal,marine or vegetable origin and these include; the acids of cocoanut,palm kernel and palm oil, also from soy bean, linseed, olive, rapeseed,cotton seed, peanut and castor oil which contain large proportions ofunsaturated hydroxy fatty acids and also the acids derived from tallow,fish and seal oils, whale or shark oils and the hydrogenated acids fromthese sources. Moreover, the synthetic high molecular weight fattyacids, obtained by the oxidation of paraffin wax and similar highmolecular weight hydrocarbons by means of gaseous oxidizing agents maybe employed. In addition the acid may be one of the resinic acids, suchas abietic acid, or the naphthenic acids and long chain fatty caidshaving an aromatic hydrocarbon radical connected directly with thealiphatic chain (Twitchell fatty acids) as are obtainable from oleic,ricinoleic, linoleic and similar unsaturated fatty acids. Instead ofemploying mixture of acids from oil, fats and resins, single acids maybe used, for example, caproic, myristic, heptylic, caprylic, undecylic,lauric, palmitic, stearic, behenic, arachic, cerotic, oleic, erucic,linoleic, linolenic, ricinoleic and hydroxystearic acids.

Of the aforesaid hydroxy diamines I prefer to employaminoethylethanolamine (C3H7NHC2H4OC2H4NHC2HOC2H4OH) but yl aminohydroxy propyl acetol amine,

(C4H9NHC3H5OHNHCH2COCH2OH) ethyl amino propanone ethanol amine,

(CzHsNHCHzCOCHzNI-ICzHrOI-I), respectively, hereinafter referred to asreactants B, C, D,

- E, F, and G.

The reactants A-G respectively may be produced by employing a number ofdifferent classical methods Well known to the art. One method consistsessentially in reacting ammonia with a compound which is the dichlorideof the R2 group between the two nitrogens and has formula Cl-Rz- Cl, andsubsequently treating the diamine produced with caustic soda to removeHCl which is attached. Then the resultant diamine is reacted with acompound of the formula ClRz-OH--, and if R1 is other than hydrogen,another reactant R1-Cl is used. Again, the hydrochloride is removed. Inthis manner, the various hydroxy diamines employed in the production ofmy starting materials maybe produced and are of the following formula:

in which R1 and R 2 have heretofore been. defined.

One of the well-known commercial methods employed in the production ofsaiddiamines whose general formula is above set forth is predicated uponthe reaction of epoxy compounds, such as, ethylene oxide, propyleneoxide, etc., with ammonia to form the intermediate diamine, which issubsequently reacted with additional epoxy compound inthe presence ofwater.

Among some of the salts of the halo acids which may be employed are thesodium and potassium salts of. monochloracetic' acid, monochlorpropionicacid, monochlorlactic acid, monochlorhydroxyacetic acid; obtainable fromdi-chloraceti'c acid, monochloracetoacetic acid, monochlorethoxyaceticacid, etc.

One of the general types of method which may be employed for theproduction of some of these starting materials consists in firstreacting one mol of a monocarboxylic acid having at. least 4 carbonatoms in its radical connected to its COOH group with one moi of one ofsaid hydroxy diaminesjexamples of which are reactants A -G, until onlyapproximately 1 mol of water has been removed. In carrying out thisreaction the mixture is first heated to about l10-180 C. in vacuum of90-130 mm. of mercury pressure until one mol of Water ofreaction has.been produced and removed. (All of the terms mm. and mm. pressure asused in this entire description are intended to mean mm. of mercurypressure.) The reaction mass is then allowed to cool to room temperatureand is then at elevated temperatures reacted withv a monohalocarboxylicacid in the presence of 4 'mols of caustic soda in aqueous solution.111.0116 of its preferred forms one mol of said reaction mass is addedto anaqueous solution containing two mols of the monohalocarboxylic and4 mols of caustic soda, which solution prior to the addition has beenprepared and maintained at a temperature nOgreater than'ZO" C The mix'isheated to a temperature of 95 C. until the-p17];

has been reduced from about 13 to 8 8.5 and the re is no further change.in pH upon continued-heating at said temperature. Another method whichmay be employed forproduo, ing some starting materials of Formula Iinthe'practice of this invention is as follows: i M v i The reactionmass of the monocarboxylic acid and the hydroxy diamine, an example ofwhichis product X, is heated to 90l 00 C. andthere is gradually added;there#,

to a 'di molecular proportion of monohalomonocarboxylic acid," such asmonochloracetic acid, whereupon .exothermic reaction occurs and thetemperature rises -from 90-100" Cfto about 130460 c. The resuIta nt isal lowed to cool to lOQ C. and is then dissolved in water.

To this solution is added an. aqueoussolution contain ing 2 mols ofcaustic soda for each molof monochloracetic acid'previously used. Thismass is stirred for about 15 minutes at a temperature of about 60 C;Theresultant product is a reaction product. as. defined in Formula I.

X, is to react 1 mole of an acid chloride, having the general formulaRCOCl, R being heretofore defined, with one mole of the hydroxy diaminein the presence of water and caustic soda,

The following are illustrative examples given merely for the purposes ofspecifically illustrating how some of the starting materials employed inthe practice of the present invention may be produced, all parts beinggiven by weight unless otherwise specified:

EXAMPLE A 200 parts of lauric acid and 104 parts of reactant A areplaced in a reacting vessel and are heated sufficiently to melt thelauric acid whereupon an agitator located therein is started and mixesand maintains these components in mixed condition. While beingconstantly agitated the mix is heated under vacuum of about 110 mm.pressure for about 3-4 hours while gradually raising the temperature to160-170 C. During this periodv 18 parts of water have been formed anddistilled off, leaving behind a reaction mass havingan acid. number ofapproximately zero. Then this reaction mass, herein known as product X,is allowed to cool to room temperature and the entire mass is added to apreviously prepared solution produced by adding 192 parts ofmonochloracetic acid and 160 parts of caustic soda to 600 parts ofwater. This solution was prepared and maintained at a temperaturebelow20 C. before the addition of said reaction mass. This mixture is heatedto 95 C. and maintained at this temperature for 2 hours. During thisperiod the pH of the mix is reduced from approximately 13 to 8-8.5. Atthe end of this period the pH of this mass is no longer subject tochange by continued heating at said temperature and a sample of theresulting product is water soluble to a sparkling clear solution. At theend of this period the mass consists chiefly of a water solution ofoneof my starting materials, hereinafter known as product A and havingth'efollowing formula:

Employ, the same procedure as that set forth in Example A, except thatonly 96 parts of monochloracetic acid, -parts of caustic soda in 300parts of water are used, and; the resultant mass is essential-1y anaqueous solutionof a, product, herein known as product W. having thefollowing formula:

To such aqueous solution containing 389. parts of. said product W, thereis added'an aqueous solution. consisting of'40-parts of caustic sodadissolved in 40 parts. of water.- Then to said mixture there are added80.5 parts ofchlorhydrin- This mixture which at this stage is atroom'temperature-is heated over a period of 1 hour to C. The-mass issubsequently maintained at this temperature of 95 C. until there is nochange in pH, this-taking approximately 2 to 3'hours. The reactionmass-consistsessentially of anaqucous solution of .a product,hereinafter-known as product W-l, and having the formula which is thesame as that of product1W, except --th'at C2H4O-C2H4OH is substitutedfor C2H4-OH.= To the resultant solution containing approximately 400parts of product W 1, cooled toroom temperature, there is added apreviously prepared solution produced by adding 96 parts ofmonochloracetic acid and SO -parts of caustic-sodato 300parts of water.This solution was. prepared and maintained at a temperature-below-20 C;before the addition of said aqueous solution oi -product W-1.- Thismixture is heated to CrHgOCaHAOCHa-COONt! u rr-c O-I I--CrH4N C Hr-C 0 0N8.

EXAMPLE C 172 parts of capric acid and 104 parts of reactant A areheated and reacted under the same condition as given in Example A, and240 parts of the reaction mass produced thereby are introduced into asolution of 220 parts of monochlorpropionic acid and 160 parts ofcaustic soda in 600 parts of water prepared and maintained below 20 C.The resulting mixture is then heated under the same conditions asoutlined in Example A until the resulting product forms sparkling clearaqueous solutions and is no longer subject to pH change in continuedheating. At the end of this period the mass consists chiefly of anaqueous solution of one of my starting materials, hereinafter known asproduct C, and having the formula the same as product A, except thatC9H19 is substituted for C11H23 and C2H4 for each CH2 therein.

EXAMPLE D 282 parts linseed fatty acid and 104 parts reactant A aretreated in the same manner as described in Example A. The entire reactonmass is then processed with an aqueous solution of 192 partsmonochloracetic acid and 160 parts of caustic soda previously made andmaintained below 20 C. and subsequently processed in the manner ofExample A to produce starting material, hereinafter known as product D,and having the same formula as that of product A, except that Ci'zHsi issubstituted for CnHzs therein.

EXAMPLE E 116 parts of caproic acid and 104 parts of reactant A arecondensed in the manner as described in the previous examples and theresulting reaction mass is subsequently processed in the same manner asthat set forth in the processing of that of Example A.

The reaction product has the same formula as that of Example A, exceptthat CsHn is substituted for CuHzs therein, and is hereinafter known asproduct E.

EXAMPLE F hereinafter known as product F.

EXAMPLE G 290 parts of dodecyl beuzoic acid and 104 parts of reactant Aare condensed in the manner described in Example D and the resultantmass is processed in the manner of Example D, whereby there is produceda novel compound having the same formula as that of Example A, exceptthat C12H25C6H4 is substituted for CuHza therein, and is hereinafterknown as product G.

6 EXAMPLE H 228 parts of myristic acid and 104 parts reactant A arereacted in the manner described in Example D and the resultant mass isprocessed in the manner of Example D, whereby there is produced astarting material hereinafter known as product H, and having the sameformula as that of Example A, except that C13H27 is substituted forC11H23 therein.

Still another type of method may be employed to produce some of thesecompounds, and examples thereof are shown hereinafter merely in anillustrative and not in a limiting sense.

EXAMPLE I 1 mol of lauric fatty acid and 1 mol of ethylenediamine(:NH2C2H4NH2) are added together and then heated in the presence of aninert solvent such as toluol in amounts sufiicient to dissolve the same.This solution is maintained at a temperature of approximately 110 C.This heating is carried out under a condenser through which pass vaporswhich consist of some of the solvent and water of reaction as well assmall amounts of unreacted amine. These products are caught in acollector from which the water of reaction is removed and the condensedtoluol and collected amine are returned to the reacting vessel. Thetemperature of the mass is maintained at 110 C. under the aforesaidconditions until 0.9 mol of Water is collected. Then a vacuum ofapproximately mm. of mercury is applied to the reacting vessel and thetemperature maintained at C. until all of the solvent and an additional0.1 mol of water have been removed. To the resulting mass is added 1 molof monochloracetic acid and this mixture is heated to a temperature ofapproximately C., whereupon the temperature of the mass willspontaneously rise to C. By the application of ex! ternal heat the massis maintained at said temperature at approximately 170 C. until a onepart sample thereof when dissolved in 100 parts of aqueous solution ofsodium hydroxide having a pH of approximately 9 provides a clearsolution. 1 mol of this mass so produced is added to an aqueous solutioncontaining 1 mol of sodium hydroxide. The entire mass is heated toapproximately 80 C. whereupon there is formed the sodium salt of saidmass, having the following formula:

The aforesaid salt, Whose structural formula is shown in this examplemay be produced in still another way. Instead of adding themonochloracetic acid at the stage previously shown, there first may beprepared an aqueous solution containing 2 mols of sodium hydroxide andone mol of monochloracetic acid. The temperature of this solution isreduced below 15 C. and preferably 5 to 10 C. and while maintained atsaid reduced temperature and being constantly agitated there is addedthereto one mol of the lauric acid-ethylene diamine reaction mass. Whilebeing constantly agitated, the temperature of the mass is raised over aone-hour period to about 95 C. Then the temperature of this constantlyagitated mass is maintained at 95 C. for an additional 3 hours or untila sample thereof in 100 parts of water will be clear and the pH is nolonger subject to change on further heating of the mass at thattemperature.

1 mol of the last defined compound is added to a solution containing onemol of caustic soda and one mol of ethylene chlorhydrin dissolved inwater at a temperature not exceeding 15 C. and preferably between 5 to10 C. After the addition at said low temperature, the mass iscontinuously agitated and while in the state of agitation itstemperature is raised over about a one hour period to 95 C. and isfurther continuously agitated and maintained at said temperature for anadditional 3 hours, all of this being done under a refiux condenser.During said 3 hour period, the pH of the mass continuously decreases. Atthe expiration of that 4 hour period the pH of 1 part of the mass whendissolved in 100 parts of Water will be 8.5. The 1 part sample whendissolved in 100 parts of water and having a pH of 8.5 in the water,provides a clear solution of product of the following formula:

C Has-C O-NH-C 2H4-N OHz-COONa Said mass, being an aqueous solutioncontaining approximately 365 parts of said compound, is cooled to roomtemperature.- Then there -is prepared at a temperature of 5 to C. anaqueous solution consisting of 96 parts of monochloracetic acid and 80parts of sodium hydroxide and 300 parts of water. While constantlymaintaining said solution in said temperature range, and while beingconstantly stirred, said aqueous solution of said compound is slowlyadded thereto. While being constantly agitated, the temperature of themass is raised over a one-hour period to approximately 95 C. Then thetemperature of this constantly agitated mass is kept at 95 C. for anadditional 3 hours or until a sample thereof in 100 parts of water willbe clear, and the pH is no longer subject to change on further heatingof the mass at that temperature. The resultant product so produced isthe same as product A heretofore identified in Example A. EXAMPLE K Byfollowing the same procedure as that set forth in Example I with theonly difference being that one mol of glycerine chlorhydrin(CH2C1"CHOH-CH2OH) is substituted for the mol of ethylene chlorhydrinthere is produced' another one of my starting materials, hereinafterknown as product K, and having a formula the same as product A, exceptthat CH2CHOHCH2O'CH2COON21 is substituted for the --C2H4OCH2COONathereof.

EXAMPLE L By following the same procedure as that set forth in Example Iwith the only difference being that one mole of pentaerythritolchlorhydrin (CH2ClC(CH2DH)a) is subst-it'uted for the mol of chlorhydrinthere is produced another one of my starting materials, hereinafterknown as product L, and having a formula the same as product A, exceptthat CH2C(CH2OH)2CH2GCH2COONa 'is substituted for -C2H4OCHzCOONathereof.

EXAMPLE M By following the same procedure as that set forth in Example Jwith. the only difference being that one mol of dimethylhydroxy ketonechlorhydrin (CICH2.COCH2OH) is employed instead of the one mol ofmonochlorhydrin there is produced another one of my starting materialshereinafter known as product M, and having a formula the'sa'meas productA, except that -CH2COCH2OCH2COONa is substituted for the thereof. Theketone employed in this example maybe preparedb'y employing thewell-known method consisting essentially of the distillation of 2 molsof hydroxy acetic acid with one mol of calcium carbonate after which theketone is chlorinated to provide the above reactant.

EXAMPLE N By'following thesamep'rocedure as that set forth in Example-Iwith the onlydifference being that, instead of employing one mol ofmonochlorhydr'in, there is employed one mol of the following compound:

OH OlGHzOOCH there is produced another one of my starting materials,hereinafter known as product N, and having the same formula as that ofproduct A, except that CH2COCHOHOCH2CO0Na is substituted for theC2H4OCH2CO0Na thereof. The particular ketone reactant employed in thisexample may be produced by the distillation of one mol of dihydroxyacetic acid, one mol of hydroxy acetic acid and one mol of calciumcarbonate after which the distillation product is chlorinated.

EXAMPLE P By following the same procedure as that set forth in Example Awith the only difference being that 2 mols of monochlorlactic acid areemployed instead of the 2 mols of monochloracetic acid so that there isproduced still another of my starting materials, hereinafter known asproduct P, having the sanie formula as product A, except thatCHzCHOHCOONa is substituted for CHaCOONa of product'A.

EXAMPLE Q Employing the same procedure as that set forth in Example A,except that 1 mol of capric acid and 1- mol of reactant B and 2 mols ofmonochlorpropionic acid are substituted for the lauric acid, reactant Aand monochloracetic aci'd', so that there is produced a startingmaterial, hereinafter known as product Q, having the following formula:

Employing the same procedure as that set forth in Example A,.- exceptthat 1 mol of stearic acid, 1 mol of reactant C, and 2 mols ofmonochlorlactic acid are employ'e'd in place of the lauric acid,reactant A and monochloracetic acid, there is provided a startingmaterial, hereinafter known as product R, having the following formula:

CllHs H CH3 C-CHa G11H;5'O0N-(|3OH2N orn-o-onzonon-ooom CH3OHzCHOH-COONa EXAMPLE S Employing the same procedure as that set forth;in Example'A, except that 1 mol ofmyristic acid, 1 mol of reactant' Dand 4 mols of potassium hydroxide are used in place of the lauric acid,reactant A and caustic soda, to provide starting material, hereinafterknown as product S, having the following formula:

H omononom-o-orn-ooox C13H27-CO-llT-CHzCHOHCHz-N CHt-COOK EXAMPLE TEmploying the same procedure as that set forth in Example A,ex'ceptthatl mol of capric acid, 1 mol of reactant E, and 2 mols" ofmonochlorethoxyacetic acid are used in place of the lauric acid,reactant A and monochloracetic acid to provide starting material,hereinafter known as product T, having the following formula:

CsH1 CsHsOczHrO-CzErOCHr-COONB.

C9H1a-C O-NC2H4OC2H4N (321140 CHE-C ONE. EXAMPLE U Employing the sameprocedure as that set forth in Example T, except that 1 mol of oleicacid, 1 mol of reactant F and 2 mols of monochloracetoacetic acid inplace of the lauric acid, reactant A and monochloracetic acid to providestarting material, hereinafter referred to as product U, having thefollowing formula:

04H CHzCOCHrO-CHzCOCHsCOONH.

CnHzz-CO-N-CHzCHOHOHrN ouzoo'om-oooNa EXAMPLE V Employing the sameprocedure as that set forth in Example A, except that in place of thelauric acid, reactant Aand caustic soda, substitute 1 mol ofdodecylbenzenemonocarboxylic acid (C12H25CaH4--COOH) 1 mol of reactant Gand 4 mols of potassium hydroxide, to provide starting material,hereinafter known as product V, having the following formula:

C'HPCOOK The specific monocarboxylic acids, as well as the spe cificmonohalomonocarboxylic acids employed in certain examples, may bereplaced by others as may be the various other reactants in the specificexamples to provide a great number of other starting materials, whichdiffer from those set forth in the examples heretofore set forth.

Prior to this invention, it was known that cationic surface activeagents and anionic surface active agents when together in aqueoussolution resulted in the production or formation of water insolublecompounds, and that adding an anionic surface active agent to an aqueoussolution of another anionic surface active agent resulted in a merephysical combination of said agents and that no reaction would occurbetween them.

Said amino acid metal salts" normally behave anionically in aqueoussolutions'having a pH above 7, and consequently it was expected thatsaid amino acid metal salts when in aqueous solution together withanionic surface agents that they would be combined physically only andthat no chemical reaction would occur therebetween. In the course of myexperimentations, I have discovered that said amino acid metal saltscould be reacted with certain anionic surface active agents at a pHabove 7 to produce water-soluble reaction products. Not only did I makesaid discovery, but I further discovered that water solutions of suchreaction products had viscosities greater than corresponding aqueoussolutions of the amino acid metal salts and also exhibited betterfoaming characteristics than did said amino acid metal salts in very lowdilutions under extreme water hardness conditions. Said reactionproducts are nontoxic and non-irritating to the human skin. They havebeen found eminently useful as general utility detergents, such as forcar washing, dish washing, clothes washing, etc. Said amino acid metalsalts when used as components of shampoos sometimes caused slightirritationor stinging of the eyes when such shampoos were used and Watersolutions thereof accidentally reached the eyes. I have furtherdiscovered that the reaction products of this invention causedpractically no irritation or stinging of the eyes when so employed.

'10 According to this invention, one or a combination-of two or more ofsaid amino acid metal salts? of the general structural Formula I arereacted with one or. a combination of two or more anionic surface activeagents of the following general structural Formula II to provide novel,water-soluble compounds having the following general structural FormulaIII, and having high wetting, detergency and surface active propertiesand capable of providing voluminous and stablefoams in aqueoussolutions, and which aqueous solutions are substantially non-irritatingto. the skin and eyes of normal human beings.

Formula II Formula III wherein R3 is a hydrocarbon radical, eitheraliphatic containing 6-18 carbon, or aliphatic-aromatic consisting of abenzene ring or a naphthalene ring having an aliphatic radical of 618carbon atoms attached thereto; X is 0803 or S03; and R, R1, R2 and Mhave been heretofore defined in Formula I.

According to this invention, I react a compound of Formula I with acompound of Formula II to provide the novel and highly useful compoundsof Formula III. In general this reaction is carried out in a solutioncontaining compounds I and II and to which a quantity of an acidic agentsuch as a strong mineral acid, as for example hydrochloric, sulphuric orits equivalent, has been added to lower the pH of the solution to avalue of approximately 7 to approximately 9 and while maintaining themass at a temperature between approximately -200F. In this reactionunder the aforesaid conditions, the compounds of Formula III areproduced, said compounds having high water solubility in spite of thefact that the number of carbon atoms in R3 is 6 or more. Such compoundsof Formula III have an unexpected extremely high water-solubility, whilethe corresponding salts of cationic compounds are water-insoluble. Theresultant aqueous solution canbe used directly as a surface activeagent, wetting agent or detergent for the purposes indicated for the.amino acid metal salts. While the quantities of the compound of FormulaI and compound of Formula 11 may be equimolecular for good yield ofcompounds of Formula III, I may employ an excess of either, and ingeneral the mole ratio of a compound of Formula I to compound of FormulaII may be 2 moles of the former to 1-3 moles of the latter.

One of the specific methods which I prefer to employ in carrying out anaspect of this invention is to first dissolve a compound of Formula I inwater and then the the pH thereof is adjusted to approximately 12-13(measured electrically) by the addition of aqueous caustic soda ifrequired so that when a compound of Formula II is added thereto, the pHof the solution of I and II Will be at least 10 and generally -11. Thetemperature of said solution is raised to 100-200 F. and preferably infactory practice to approximately l40 F. Then a quantity of a compoundof Formula II is dissolved in water in a separate container and thissolution is added tosaid firstsolution and the mass is maintained insaid temperature range while being constantly stirred, and an acidicagent is added thereto to reduce the pH thereof to a value below 10 andin the range i An'aqueous solution of 500 parts ofproduct A in 750 partsof water is heated to approximately 140 F. and its pH (measuredelectrically) is adjusted by the addition of aqueous caustic soda to12-43. While being constantly stirred and maintained at thattemperature, there is added a solution of 290 parts of sodium salt oflauryl sulfate:

' C12H25-'O-'-SOs-Na in 450 parts of water. Then while stirring and thetemperature is maintained, there is added thereto between about 30-40parts of hydrochloric acid solution (32%), whereby the pH of the mass islowered to a value in the range of 8.2 to 8.7. Stirring is continued andthe temperature maintained for about 10 minutes more. The resultantproduct .is a solution of the novel reaction product having thefollowing formula:

C2H4-OCH2-COONH 011112343 O-I\IIC zH4N H GET-000m C 2H2s'O-SO3 EXAMPLE 2Employ the same procedure and components as set .forth in Example 1,except that only about 150 parts of the sodium salt of lauryl sulfateare used. 7 In this instance, the resultant product is a solution of thenovel reaction product whose structural formula is shown in Example 1together with unreacted product A used, in the approximate proportion oftwo parts of the former to one of the latter. 7

Employ the same procedure as that set forth in Example 1, but employ thecomponents indicated in the following EXamples 3-36; the quantity ofhydrochloric acid solution (32%) is variable to lower the pH to valuesindicated in Example 1 to obtain the novel reaction prodnets of saidExamples 3-36.

EXAMPLE 3 500 parts of product A in 750 parts of water. parts of stearylsulfonate sodium salt:

in 700 parts of water.

FORMULA OF NOVEL REACTION PRODUCT I C2H O-CHrCOONa OirHrs- C ON-C 2H4N HH2OO ONa CraHar-SO:

EXAMPLE 4 450 parts of product C in 700 parts of water. parts of dodecylbenzene sulfonate sodium salt:

EXAMPLE '5 500 parts of product A in 750 parts of water. 300 parts of:hexylnaphthene sulfonate sodium salt:

in 450 par-ts of water.

FORMULA OF NOVEL REACTION PRODUCT CtHrs CHr-COONB EXAMPLE 6 500 parts ofproduct Q in 800 parts of water.

parts of hexyl sulfate sodium salt:

C6H13-OSO3N3.

in 400 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CH CH3 CHr-CH-O-CzHr-CO 0m- 0 sHw- S O3 EXAMPLE 7 660 parts of product R in 1,000 parts of water.

parts of decyl benzene sulfonate sodium salt:

C1oHz1C6H4SO3Na in 600 par-ts of'water.

FORMULA OF NOVEL REACTION PRODUCT H I CuHu-C O-N-C (CH3) 2CHrN ooHmo'Hz-o-ornorromoo'oNa onionon-ooom CmHn-CsHt- 03 EXAMPLE 8 550 partsof product S in 850 parts of water.

parts of octyl benzene sulfate potassium salt:

CaH1'1-CsH4SOsK in 500 parts of water.

FORMULA OF NOVEL REACTION PRODUCT CHz-COOK parts of decyl sulfate sodium salt:

in 600 parts of water.

Cat n-S 0a .CzHr'O oinr-o-oinro (3111-0 0 O'Na CaH4'0 C'Hi-CO ONE to A13 EXAMPLE 675 parts of product U in 1,000 parts of water. parts ofheptyl benzene sulfonate sodium salt;

C7H15-CcH4SO3-Na C1sH27SOsNa in 450 parts of water.

FORMULA OF NOVEL REACTION PRODUCT C2115 021140 CHz-COOK C12H25-CaH4-CO-N-CH2C QCHz-N H CHr-C O O K CraHzr-S O EXAMPLES 12-16 Employing thesame procedure as that set forth in Example 1, except that products B,K, L, M, and N are respectively substituted for product A to provideother novel reaction products.

EXAMPLES 17-20 Employing the same procedure as that set forth in Example1, except that products D, E, G, and H are respec- 5 tively substitutedfor product A to provide novel reaction products, which differ from thenovel reaction product whose formula is shown in Example I, bysubstituting for the C11H23 radical thereof the following respectiveradicals: C1'IH31, CsHn, C12H25-C6H4 and C13H2'z.

EXAMPLE 21 Employing the same procedure as that set forth in Example 1,except that product P is substituted for prodnot A to provide a reactionproduct which differs from the novel reaction product, whose formula isshown in Example 1, by substituting for the CHz--COONa radical thefollowing radical: CH2--CHOH--COONa.

EXAMPLES 22 and 23 Employing the same procedure as that set forth inExample 1, except that products C and F respectively are substituted forproduct A to provide novel reaction products which differ from the novelreaction product whose formula is shown in Example 1, by substitutingC2H4COON3 for the CHz-COONa and also substituting C9H19 and C17H35respectively for CuHzz.

EXAMPLES 24-36 6O Employing the same procedure as that set forth inExample 3, except that, instead of product A, there are respectivelysubstituted compounds which are the same as product A, except that the Hof the NH attached directly to the CO group thereof is replaced by thefollowing respective radicals: -CH3, C2H5, C3H7,

CHOHCHOHCH2OH, C2H4OCH3, C2H4OC2I-I4OH, CH2CHOHOC2H5, -CH2COCH3,C2H4COC2H4OH, --CH2OHCOC2H5; whereby there are produced a number ofother novel reaction products whose formulas are the same as the formulaof the novel reaction product whose formula is within the definition ofFormula III and shown in Example 3, except that the aforesaid respectiveradicals replace the H of the NH connected directly to the CO thereof.

Following the same procedure as that set forth in Example 1 andemploying 1 mol of any of said other starting materials of Formula Irespectively, and 1 mol of any of the other specific compounds ofFormula II employed in Examples l-36, a great number of other novelreaction products whose formulas are that of Formula III may beproduced; and in addition, the specific reactants employed may difierfrom those employed herein, in varying R, R1, R2, and R3 within thedefinitions thereof, to provide a great number of other compounds ofFormula III.

It is to be understood that instead of first adjusting the pH of thecompound of Formula I to 12-13 before the addition of the compound ofFormula II, any other method may be employed to obtain the conditionwhereby the pH of the solution of I and II is at least 10 and preferably10.5-11 before the addition of the acidic agent to lower the pH of themass to approximately 7 to approximately 9. For example, I and II may bedissolved together and this solution may, by the addition of causticsoda when required, have its pH adjusted to at least 10, and then at.l00-200 F.. is ready for the addition of the acidic agent to lower itspH to approximately 7 to approximately 9. If desired, the requiredamount of acidic agentmay be added either before or after the solutionof pH of at least 10 is brought to a temperature in the range of -200 F.

Since certain changes in carrying out the aforesaid processes andcertain modifications in the compositions which embody the invention maybe made without departing from its scope, it isjntended that all mattercontained in the description shall be interpreted as illustrative andnot in a limiting sense. 3

It is also to be understood that the following claims are intended tocover all the generic and specific features of the invention hereindescribed, and all statements of the scope of the invention which as amatter of language might be said to fall therebetween.

I claim:

1. A compound of the following formula:

in which R is a hydrocarbon radical of 4-18 carbon atoms; R2 is anorganic group selected from the class consisting of (a) aliphatichydrocarbon groups of l-4 carbon atoms; (b) hydroxy substitutedaliphatic hydra carbon groups of l-4 carbon atoms, (0) aliphatic ethergroups, each of said ether groups having at least one ether oxygenlinkage therein and otherwise being hydrocarbon of 24 carbon atoms, (d)aliphatic ether groups, each of said groups having at least one etheroxygen linkage therein and otherwise being hydroxy substitutedhydrocarbon of 2-4 carbon atoms, (e) aliphatic keto groups, each of saidgroups having at least one carbonyl linkage therein and otherwise beinghydrocarbon of 2-4 carbon atoms, (1) aliphatic keto groups, with each ofsaid groups having at least one carbonyl linkage therein and otherwisebeing hydroxy substituted hydrocarbon of 2-4 carbon atoms, (g) aliphaticgroups having keto carbonyl and ether oxygen linkages therein, andotherwise being hydrocarbon of 34 carbon atoms, (h) aliphatic groups,each of said groups having keto carbonyl and ether oxygen linkagestherein and otherwise being hydroxy substituted hydrocarbon of 3-4carbon atoms; R1 is selected from the group consisting of hydrogen andmonovalent radicals otherwise defined in said (a)-(h); R3 is ahydrocarbon radical selected from the class consisting of (i) aliphatichydrocarbon radicals of 618 carbon atoms and (j) aliphatic-aromatichydrocarbon radicals consisting of henzene and naphthalene groups, eachgroup having an aliphatic hydrocarbon radical of 6-18 carbon atomsattached 15 i6 theretoaX is selected from the group. consisting. of S035. A compound of the following formula: and 0803; and M is an alkalimetal. I H CQHPOAJHAQCcma 2. A compound of the following formula: l

. CnHzs-C O-NC2H4N CzH4O OHz-C O ONa .l 5 H CHr-COONa R-C O-N-C 2H4YN Hong-000m R3X in which R3 is an aliphatic hydrocarbon radical of 6-18Rafix carbon atoms and X is selected from the group of S03 and in whichR is a hydrocarbon radical of 4-18 carbon atoms m 0803. and R3 is analiphatic hydrocarbon radical of 6-'18 carbon 6. A compound of thefollowing formula: atoms, and X is selected from the group consisting ofS03 H OONa and 0803; I

3. A compound of. the following formula: magi-C O N C=H-N C2HO-oH,o0'oNa OHr-COONa R'-CO- I IC=H4'-N it CIBHWTSOQ H CH'i-COONa 7. Acompound of the following formula:

803 1?: C2H4O-CH2COON1 C9H19-G O-NCzH4-N n entire 0 ONa in which R is ahydrocarbon radical of 4-18 carbon atoms and R4 is an aliphatichydrocarbon radical of 6-18 carbon atoms. C EH25 4. A compound of thefollowing formula:

H oimnonoflrooom 8. A compound of the following formula: R-C o-1ir-Cn2u-I I CQHAOCHr-COONQ n 'er'rrooom 3o clin y-w ON-C2H4N a so, H oH oooN-aReferences Citedin the file of this patent UNITED STATES PATENTS inwhichR is a hydrocarbon radical of 4-1-8 carbon atoms 2,103,872 SchoellerDec. 18, 1937 and R4 is an aliphatic hydrocarbon radical of 6-18 carbon2,329,406 Mauersberger Sept. 14, 1943 atoms.

1. A COMPOUND OF THE FOLLOWING FORMULA: